CN114874463A - Anti-freezing conductive hydrogel with excellent mechanical properties and preparation method and application thereof - Google Patents
Anti-freezing conductive hydrogel with excellent mechanical properties and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 230000008014 freezing Effects 0.000 claims abstract description 33
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- 239000002135 nanosheet Substances 0.000 claims abstract description 26
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- 238000000034 method Methods 0.000 claims description 19
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
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Images
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2405/04—Alginic acid; Derivatives thereof
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- C08K3/14—Carbides
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Abstract
The invention provides a preparation method of an organic anti-freezing conductive hydrogel with excellent mechanical properties, which is characterized by comprising the following steps: s1: providing a double-network hydrogel precursor liquid; s2: providing titanium carbide nanosheets; s3: providing an organic cryoprotective solution; s4: combining the double-network hydrogel precursor liquid with a titanium carbide nanosheet to obtain a conductive double-network hydrogel; s5: adding halide into the organic freezing protection solution to obtain a halide organic freezing protection solution; s6: and soaking the conductive double-network hydrogel in a halide organic freezing protection solution for solution replacement to obtain the organic anti-freezing conductive hydrogel with excellent mechanical properties, wherein the tensile breaking elongation of the organic anti-freezing conductive hydrogel is more than 800%, the conductivity of the organic anti-freezing conductive hydrogel is higher than 0.9S/m, and the freezing temperature of the organic anti-freezing conductive hydrogel is lower than-60 ℃.
Description
Technical Field
The application belongs to the field of hydrogel materials, and particularly relates to an anti-freezing conductive hydrogel with excellent mechanical properties, and a preparation method and application thereof.
Background
Hydrogels are a class of very hydrophilic three-dimensional network-structured gels that swell rapidly in water and in this swollen state can hold a large volume of water without dissolving. Due to its excellent stretchability, water absorption and biocompatibility, hydrogels are currently being extensively studied and applied in biomedical, environmental protection, energy storage, etc.
The hydrogel contains three existing forms of water, namely free water, weak bonding water and strong bonding water. Generally, the hydrogel contains most of free water, which means that when the hydrogel is in a subzero temperature environment, the free water freezes, causing the hydrogel to become hard and brittle, losing its original mechanical properties, electrical conductivity, etc., and greatly limiting the application field of the hydrogel. Therefore, the problem of solving the problem of freezing of free water in the hydrogel so as to improve the anti-freezing performance of the hydrogel is a problem which needs to be researched urgently. At present, two approaches are generally used for improving the freezing resistance of hydrogel, one is to introduce a cryoprotectant into the hydrogel, for example, patent publication CN110054784A provides a self-healing anti-freezing conductive fibroin hydrogel and a preparation method thereof, and a glycerol cryoprotectant is introduced into the hydrogel to reduce the freezing point of the hydrogel. However, the electrical properties of the hydrogel are greatly influenced because the cryoprotectant is not beneficial to ion migration; secondly, inorganic salt is introduced into hydrogel by utilizing hydration of metal ions to improve the freezing resistance of the hydrogel, for example, in patent publication CN1284758, a preparation method of a gel electrolyte for a freezing-resistant zinc-based battery is provided, zinc salt and sodium salt are introduced into the hydrogel to enhance the freezing resistance and the electrical property of the hydrogel, but the mechanical property of the hydrogel is generally poor.
Therefore, the balance of the mechanical property, the anti-freezing property and the electrical conductivity of the hydrogel is a research direction with great application prospect and significance.
Disclosure of Invention
Based on the above problems, the present invention aims to provide a method for preparing an anti-freeze conductive hydrogel with good tensile properties, wherein the hydrogel is prepared from a polymer monomer, an initiator, a cross-linking agent, a conductive filler and a multi-component system consisting of water, a cryoprotectant and a halide. According to the preparation method, the polymer network chain formed by the reaction of two different monomers is wound and unwound, so that the breaking elongation of the prepared hydrogel is more than 800%, the hydrogel can not be cracked under the condition of more than 80% of strain pressure, and the hydrogel can still be quickly and basically recovered to the original shape after the pressure is removed; the existence of the titanium carbide nanosheet and halide enables the conductivity of the prepared hydrogel to be more than 0.9S/m; the molecular replacement of halide freezing protection solution in the solution replacement method is utilized to reduce weak bound water and increase strong bound water in the hydrogel, so that the freezing temperature of the hydrogel is lower than-60 ℃, and experiments prove that the hydrogel still has elasticity at-60 ℃, can be stretched, bent and twisted without fracture and unrecoverable deformation, is applied to monitoring the movement of muscles and joints of a human body, and lays a foundation for the application of the hydrogel in the fields of flexible manufacturing, intelligent sensing, biomedical treatment and the like.
In order to achieve the above objects, the present application proposes a method of preparing an organic anti-freeze conductive hydrogel having excellent mechanical properties, comprising the steps of:
s1: providing a double-network hydrogel precursor liquid;
s2: providing titanium carbide nanosheets;
s3: combining the double-network hydrogel precursor liquid with the titanium carbide nanosheets to obtain a conductive double-network hydrogel;
s4: providing an organic cryoprotective solution and a halide; mixing the organic freezing protection solution with the halide to obtain a halide organic freezing protection solution;
s5: and soaking the conductive double-network hydrogel in the halide organic freezing protection solution for solution replacement to obtain the anti-freezing conductive hydrogel with excellent mechanical properties.
In one embodiment, the double-network hydrogel precursor solution is a sodium alginate-polyacrylamide hydrogel precursor solution, and the step S1 includes:
s101: providing sodium alginate and acrylamide, mixing the sodium alginate and the acrylamide in deionized water, and stirring to obtain a first clear liquid, wherein the mass ratio of the sodium alginate to the acrylamide is 1: 4-4: 1;
s102: providing a cross-linking agent and an initiator, adding the cross-linking agent and the initiator into the first clarified liquid to obtain a second clarified liquid, wherein the mass ratio of the cross-linking agent to the initiator to the sodium alginate is 1: 1-4: 1,15: 1-30: 1.
in one embodiment, the cross-linking agent is at least one of tetramethylethylenediamine, N' -methylenebisacrylamide; the initiator is at least one of ammonium persulfate, sodium persulfate and potassium persulfate.
In one embodiment, the step S2 includes:
s201: providing an etching solution and titanium aluminum carbide, adding the titanium aluminum carbide into the etching solution, uniformly mixing, reacting at the rotating speed of 400-1400 rpm for 5-20 min to obtain a first mixed solution, wherein the concentration of the titanium aluminum carbide in the first mixed solution is 0.01-0.25 g/L;
s202: and transferring the first mixed solution into a heater at the temperature of 25-60 ℃, condensing and refluxing at the stirring speed of 100-600 rpm, and etching to obtain the titanium carbide nanosheet dispersion.
In one embodiment, the step S3 includes:
s301: transferring the second clarified liquid into a reaction container, and mixing the second clarified liquid with the titanium carbide nanosheets to obtain a second mixed solution, wherein the mass ratio of the sodium alginate to the titanium carbide nanosheets is as follows: 1: 5-1: 1;
s302: putting the second mixed solution into a vacuum drier, and vacuumizing for 40-80 minutes to remove bubbles to obtain a third mixed solution;
s303: transferring the third mixed solution into a mold, and putting the mold into a water bath to perform thermal polymerization for 40-80 min to obtain the conductive double-network hydrogel, wherein the thermal polymerization temperature is 40-90 ℃;
in one embodiment, the organic cryoprotectant solution is a mixed solution of cryoprotectants in deionized water, and the mass ratio of the cryoprotectant to the deionized water is 1: 1-5: 1; the cryoprotectant is at least one of ethylene glycol, glycerol and sorbitol.
In one embodiment, the halide is at least one of lithium chloride, calcium chloride, and sodium chloride.
In another aspect of the present invention, the preparation method of any of the organic anti-freeze conductive hydrogels with excellent mechanical properties described in the previous paragraphs is claimed to obtain fast-gelling hydrogels.
In a further aspect of the present invention, the application of the aforementioned organic anti-freeze conductive hydrogel with excellent mechanical properties is claimed, and the application fields thereof comprise: environmental protection, energy storage, tissue engineering, tissue repair, human-computer interface and brain-computer interface.
The preparation method has the advantages that the breaking elongation is 820-1210% by winding and unwinding the sodium alginate chain and the polyacrylamide chain, the sodium alginate chain and the polyacrylamide chain can not be cracked under the condition of more than 80% of strain pressure, and the sodium alginate chain and the polyacrylamide chain can still be quickly and basically recovered to the original shape after the pressure is removed; the conductivity of the titanium carbide nanosheet and the halide is more than 0.9S/m; the molecular replacement of the halide freezing protection solution in the solution replacement method is utilized to reduce weak bound water and increase strong bound water in the hydrogel, the freezing temperature of the hydrogel is lower than-60 ℃, and experiments prove that the hydrogel still has elasticity at-60 ℃, can be stretched, bent and twisted without fracture and unrecoverable deformation, is applied to monitoring the movement of muscles and joints of a human body, and lays a foundation for the application of the hydrogel in the fields of flexible manufacturing, intelligent sensing, biomedical treatment and the like.
Drawings
The following detailed description of embodiments of the invention is provided in conjunction with the appended drawings:
FIG. 1 shows a schematic diagram of a method of making one embodiment of the present invention;
FIG. 2 shows stress-strain curves in tensile tests of examples 1 to 5 of the present invention and comparative example 1;
FIG. 3 shows stress-strain curves in compression tests for examples 1 to 5 of the present invention and comparative example 1;
FIG. 4 shows the electrical conductivity of examples 1 to 5 of the present invention and comparative example 1;
FIG. 5 shows a differential scanning calorimetry plot of example 4 of the present invention and comparative example 2;
FIG. 6 shows the mechanical properties of the hydrogels of the present invention in a low temperature environment;
figure 7 shows the application of the hydrogel of the invention in the detection of human joint and muscle movement.
Detailed Description
In order to clarify the invention in more detail, the technical solution of the invention is further elucidated below with reference to a preferred embodiment and the accompanying drawings.
As shown in FIG. 1, the present invention provides a method for preparing an organic anti-freeze conductive hydrogel with excellent mechanical properties, comprising the following steps:
s1: providing a double-network hydrogel precursor liquid; s2: providing titanium carbide nanosheets; s3: combining the double-network hydrogel precursor liquid with the titanium carbide nanosheets to obtain a conductive double-network hydrogel; s4: providing an organic cryoprotective solution and a halide; mixing the organic freezing protection solution with the halide to obtain a halide organic freezing protection solution; s5: and soaking the conductive double-network hydrogel in the halide organic freezing protection solution for solution replacement to obtain the anti-freezing conductive hydrogel with excellent mechanical properties. The anti-freezing conductive hydrogel with excellent mechanical properties is obtained, the tensile elongation at break of the hydrogel is more than 800 percent, the conductivity of the hydrogel is higher than 0.9S/m, and the freezing temperature of the hydrogel is lower than-60 ℃.
In some preferred embodiments, the above steps S1-S5 are performed in the order shown in FIG. 1. The preparation method has the advantages that the polymer network chain formed by the reaction of two different monomers is wound and unwound, so that the breaking elongation can be more than 800%, the polymer network chain can not be cracked under the condition of more than 80% of strain pressure, and the polymer network chain can still be quickly and basically recovered to the original shape after the pressure is removed; the conductivity of the titanium carbide nano-sheets is increased to 0.92S/m by the titanium carbide nano-sheets and the halide; the molecular replacement of the halide organic cryoprotectant in the solution replacement method is utilized to reduce weak bound water and increase strong bound water in the hydrogel, the freezing temperature of the hydrogel is lower than-60 ℃, and experiments prove that the hydrogel still has elasticity at-60 ℃, can be stretched, bent and twisted without fracture and unrecoverable deformation, is applied to monitoring the movement of muscles and joints of a human body, and lays a foundation for the application of the hydrogel in the fields of flexible manufacturing, intelligent sensing, biomedical treatment and the like.
Preferably, the double-network hydrogel precursor solution is a sodium alginate-polyacrylamide hydrogel precursor solution, and in some preferred embodiments, the sodium alginate-polyacrylamide hydrogel precursor solution is prepared by the following steps, that is, step S1 includes:
s101: providing sodium alginate and acrylamide, mixing the sodium alginate and the acrylamide in deionized water, and stirring to obtain a first clear liquid, wherein the mass ratio of the sodium alginate to the acrylamide is 1: 4-4: 1;
s102: providing a cross-linking agent and an initiator, adding the cross-linking agent and the initiator into the first clarified liquid to obtain a second clarified liquid, wherein the mass ratio of the cross-linking agent to the initiator to the sodium alginate is 1: 1-4: 1,15: 1-30: 1.
it is worth mentioning that in step S101, the sodium alginate is combined with the acrylamide to form a double-network structure in the hydrogel, and the hydrogel is endowed with excellent mechanical properties through the winding and unwinding of the chain.
In some preferred embodiments, the cross-linking agent in step S102 is selected from at least one of tetramethylethylenediamine, N' -methylenebisacrylamide, and the initiator is selected from at least one of ammonium sulfate and sodium persulfate, to further provide hydrogen bonds and sulfate groups for the reaction, to strengthen the entanglement of chains in the double-network hydrogel, and to accelerate the gel formation.
The titanium carbide nanoplates in the present application may be known in the art, or may be prepared by known methods, and may be self-adjusted according to the needs of those skilled in the art, and in some preferred embodiments, the titanium carbide nanoplates are prepared by the following steps, that is, preferably, the step S2 includes:
s201: providing an etching solution and titanium aluminum carbide, adding the titanium aluminum carbide into the etching solution, uniformly mixing, reacting at the rotating speed of 400-1400 rpm for 5-20 min to obtain a first mixed solution, wherein the concentration of the titanium aluminum carbide in the first mixed solution is 0.01-0.25 g/L;
s202: and transferring the first mixed solution into a heater at the temperature of 25-60 ℃, condensing and refluxing at the stirring speed of 100-600 rpm, and etching to obtain the titanium carbide nanosheet dispersed solution.
Preferably, the conductive double-network hydrogel is obtained by uniformly mixing and thermally polymerizing the sodium alginate-polyacrylamide hydrogel precursor solution and the titanium carbide solution, and the step S3 includes:
s301: transferring the second clarified liquid into a reaction container, and mixing the second clarified liquid with the titanium carbide nanosheets to obtain a second mixed solution, wherein the mass ratio of the sodium alginate to the titanium carbide nanosheets is as follows: 1: 5-1: 1;
s302: putting the second mixed solution into a vacuum drier, and vacuumizing for 40-80 minutes to remove bubbles to obtain a third mixed solution;
s303: transferring the third mixed solution into a mold, and putting the mold into a water bath to perform thermal polymerization for 40-80 min to obtain the conductive double-network hydrogel, wherein the thermal polymerization temperature is 40-90 ℃;
in some preferred embodiments, the cryoprotectant of step S4 is at least one of ethylene glycol, glycerol, sorbitol. The halide is at least one of lithium chloride, calcium chloride and sodium chloride.
The cryoprotective solution in the present application may be a substance known in the art or a substance prepared by a known method, and may be adjusted according to the needs of the skilled person, and in some preferred embodiments, the organic cryoprotective solution is prepared by mixing the cryoprotective agent with deionized water, wherein the mass ratio of the cryoprotective agent to the deionized water is 1: 1-5: 1. the halide concentration is 0.05 mol/L-2 mol/L in the halide freezing protection solution, and the halide is at least one of lithium chloride, calcium chloride and sodium chloride. The halide ionizes anions and cations in the organic cryoprotectant, and provides sufficient conductive substances for a subsequent solution replacement method, so that excellent conductive performance is endowed to the hydrogel.
Preferably, the conductive double-network hydrogel is soaked in the halide organic freezing protection solution for solution replacement, so that the anti-freezing conductive hydrogel with excellent mechanical properties is obtained.
The organic anti-freezing conductive hydrogel with excellent mechanical properties prepared by the preparation method utilizes the winding and unwinding of the sodium alginate chain and the polyacrylamide chain to ensure that the breaking elongation rate of the hydrogel is more than 800 percent, the hydrogel can not be cracked under the condition of 80 percent of strain pressure, and the hydrogel can still be quickly and basically recovered to the original shape after the pressure is removed; the electric conductivity of the titanium carbide nano-sheet and the halide is increased to 0.92S/m, the weak bound water in the hydrogel is reduced and the strong bound water is increased by utilizing the molecular replacement of the halide organic cryoprotectant in a solution replacement method, the freezing temperature of the hydrogel is reduced to-62.46 ℃, and meanwhile, experiments verify that the hydrogel still has elasticity at the temperature of-60 ℃, can be stretched, bent and twisted without fracture and unrecoverable deformation, and is applied to the monitoring of the movement of muscles and joints of a human body, thereby laying a foundation for the application of the hydrogel in the fields of flexible manufacturing, intelligent sensing, biological medical treatment and the like.
The preparation of the organic antifreeze conductive hydrogel with excellent mechanical properties in the present application is further illustrated below with reference to the following examples:
example 1
Dissolving sodium alginate and acrylamide in deionized water under magnetic stirring to prepare a first clarified liquid with the mass fractions of sodium alginate and acrylamide being 0.2% and 1.8%, respectively; respectively dissolving N, N '-methylene-bisacrylamide and ammonium persulfate in deionized water to obtain a cross-linking agent solution and an initiator solution, respectively adding the cross-linking agent solution and the initiator solution into the first clarified liquid, and stirring until the cross-linking agent solution and the initiator solution are uniformly mixed to obtain a second clarified liquid with the mass fractions of the N, N' -methylene-bisacrylamide and the mass fraction of the ammonium persulfate being 0.08% and 1%.
LiF is added into 9mol/L hydrochloric acid solution and stirred for 10min at room temperature to obtain etching solution with LiF concentration of 0.08 g/ml. Then slowly adding Ti 3 AlC 2 The powder was added to the etching solution to obtain a first mixed solution having a concentration of 0.05g/ml, and the mixture was stirred and reacted at 35 ℃ for 24 hours. And after the reaction is finished, obtaining a black reactant, centrifuging the obtained black reaction product for 5min, pouring out the supernatant, and repeatedly centrifuging and cleaning the precipitate for 5-6 times by using deionized water until the pH value of the supernatant is neutral. And then dispersing the precipitate with pure water, ultrasonically stripping under the ultrasonic power of 250W, and finally drying by a vacuum freeze drying oven to obtain stripped titanium carbon nano sheet powder, and storing in a refrigerator at 4 ℃ for subsequent experiments.
And mixing the titanium carbon nano sheet powder with the second clarified liquid, and uniformly stirring to obtain a second mixed liquid with the mass fraction of the titanium carbon nano sheets being 0.2%. Then, putting the second mixed solution into a vacuum drier, and vacuumizing for 40-80 minutes to remove bubbles to obtain a third mixed solution; and pouring the third mixed solution with bubbles removed into a mold, and heating the third mixed solution in water bath at the temperature of 40-90 ℃ for 40-80 min to obtain the conductive double-network hydrogel.
Preparing a freezing protective agent with the volume percentage concentration of 50% by using ethylene glycol and deionized water, adding LiCl to prepare a halide organic freezing protective agent with the concentration of 1mol/L, and soaking the prepared conductive double-network hydrogel in a solution for 1-3 hours to obtain the anti-freezing conductive hydrogel with excellent mechanical properties.
Example 2
Example 2 differs from example 1 only in that the mass fraction of titanium carbide in the second mixed liquid is 0.4%.
Example 3
Example 3 differs from example 1 only in that the mass fraction of titanium carbide in the second mixed liquid is 0.6%.
Example 4
Example 4 is different from example 1 only in that the mass fraction of titanium carbide in the second mixed liquid is 0.8%.
Example 5
Example 5 differs from example 1 only in that the mass fraction of titanium carbide in the second mixed liquid is 1.0%.
Comparative example 1
Comparative example 1 differs from example 1 only in that no titanium carbo-xide was added.
Comparative example 2
Comparative example 2 differs from example 4 only in that it is not soaked with the halide organic cryoprotectant solution.
FIG. 2 is a graph showing the stress-strain curves in the tensile test of the hydrogel samples obtained in examples 1 to 5 and comparative example 1, in which the hydrogel was cut into strips of 20 mm. times.15 mm. times.2 mm, and the tensile test was performed according to the national standard using a universal tester at a tensile speed of 20 to 40mm/min in an upward direction, and the results are shown in FIG. 2. It can be seen that the elongation at break of the organic anti-freezing conductive hydrogel with excellent mechanical properties is 820% -1210%, wherein the tensile elongation at break of the hydrogel sample obtained in example 4 can reach 1210%, which is the largest in each example, and the excellent tensile properties are exhibited.
FIG. 3 is a stress-strain curve of the hydrogel samples obtained in examples 1 to 5 and comparative example 1 in a compression test, the hydrogel is formed into a cylinder with a diameter and a height of 13mm by using a mold, a compression test is performed by using a universal testing machine according to the national standard, the test speed is 20-40 mm/min, the direction is downward, and the test stop condition is that when the material strain reaches 80%, the obtained result is shown in FIG. 3. It can be seen that example 4 also exhibits excellent mechanical properties in the compression test, with a stress of 257KPa at 80% compressive strain.
FIG. 4 is a schematic diagram showing the electrical conductivity of hydrogel samples obtained in examples 1 to 5 and comparative example 1, in which hydrogel was formed into a cylinder having a diameter and a height of 13mm using a mold, conductive wires were attached to both ends of the cylinder using conductive silver paste and copper tape, the resistance of the examples was measured using a digital source meter, the voltage was constant at 5V, and the following formula was used
The conductivity of the example is calculated, the obtained result is shown in fig. 4, and it can be seen that the conductivity of the example is gradually increased with the increase of the dosage of the conductive filler titanium carbide nanosheet, wherein the conductivity of the hydrogel sample obtained in example 5 reaches 0.92S/m, and meanwhile, the electrons ionized by the halide in the cryoprotectant, which enter the hydrogel interior through the solution replacement method, contribute to the conductivity of the hydrogel sample obtained in the example, and enhance the conductivity of the hydrogel.
FIG. 5 is a DSC analysis chart of hydrogel samples obtained in example 4 and comparative example 2, and a Differential Scanning Calorimetry (DSC) analysis test is performed on the hydrogel samples obtained in example 4 and comparative example 2, the temperature is gradually reduced from 25 ℃ to-85 ℃ during the test, the temperature reduction speed is 5 ℃/min, the obtained result is shown in FIG. 5, and it can be seen from the DSC curve that the phase transition temperature of example 4 reaches-62.46 ℃, and the icing temperature of comparative example 2 is-17.34 ℃, because the free water and the weak bound water in the original hydrogel are replaced by the halide organic refrigerant in the solution replacement method, which results in the greatly increased content of strong water in the hydrogel, and on the other hand, the entering of the organic solvent enhances the formation of hydrogen bonds with water molecules and the double-network chain hydrogel, greatly enhances the binding capacity of the hydrogel to the water molecules therein, thereby further illustrating that the halide organic freezing protective agent introduced in the application endows the hydrogel with excellent water binding capacity And (4) freezing resistance.
FIG. 6 is a deformation diagram of hydrogel samples obtained in example 4 and comparative example 2 at-60 deg.C, wherein the hydrogel samples obtained in example 4 can be stretched, twisted and bent without breaking and unrecoverable deformation in low temperature environment, while the hydrogel samples obtained in comparative example 2 become rigid and inflexible in such environment, further illustrating the enhancement and improvement of the freezing resistance of the hydrogel by the organic halide cryoprotectant.
FIG. 7 is the sensing function of the hydrogel sample obtained in example 4 on human joints and muscles, which can detect the expression changes caused by the changes of finger joints and facial muscles, and can give corresponding responses to different movements and different degrees of the same movement. Wherein, fig. 7a is the monitoring of the mouth opening and closing movements; FIG. 7b is a schematic illustration of smiling, mouth closing motion monitoring; FIG. 7c is a view of the monitoring of the finger joints bending at different angles; fig. 7d shows motion monitoring for elbow flexion and extension.
The preparation method of the organic anti-freezing conductive hydrogel with excellent mechanical properties provided by the application can be extended to the preparation of other double-network functionalized hydrogels, and on the other hand, the invention requests to protect the preparation method of any organic anti-freezing conductive hydrogel with excellent mechanical properties to obtain a hydrogel capable of being rapidly gelled.
Finally, it should be noted that: the above-mentioned embodiments are merely preferred examples for clearly illustrating the invention, but are not limited to the embodiments of the invention, and it should be understood by those skilled in the art that the technical features in the above-mentioned embodiments can be combined arbitrarily, and other modifications in different forms or equivalent replacements of part of the technical features can be made on the basis of the above-mentioned embodiments, and not all embodiments can be exhaustive, so that any modifications, improvements, equivalents and the like which are included in the technical solution of the present invention are within the technical scope of the claims of the present invention.
Claims (10)
1. A preparation method of antifreeze conductive hydrogel with excellent mechanical property is characterized by comprising the following steps:
s1: providing a double-network hydrogel precursor liquid;
s2: providing titanium carbide nanosheets;
s3: combining the double-network hydrogel precursor liquid with the titanium carbide nanosheets to obtain a conductive double-network hydrogel;
s4: providing an organic cryoprotective solution and a halide; mixing the organic freezing protection solution with the halide to obtain a halide organic freezing protection solution;
s5: and soaking the conductive double-network hydrogel in the halide organic freezing protection solution for solution replacement to obtain the anti-freezing conductive hydrogel with excellent mechanical properties.
2. The method for preparing the anti-freezing conductive hydrogel with excellent mechanical properties as claimed in claim 1, wherein the double-network hydrogel precursor solution is a sodium alginate-polyacrylamide hydrogel precursor solution, and the step S1 comprises:
s101: providing sodium alginate and acrylamide, mixing the sodium alginate and the acrylamide in deionized water, and stirring to obtain a first clear liquid, wherein the mass ratio of the sodium alginate to the acrylamide is 1: 4-4: 1;
s102: providing a cross-linking agent and an initiator, adding the cross-linking agent and the initiator into the first clarified liquid to obtain a second clarified liquid, wherein the mass ratio of the cross-linking agent to the initiator to the sodium alginate is 1: 1-4: 1. 15: 1-30: 1.
3. the method for preparing anti-freeze conductive hydrogel with excellent mechanical properties of claim 2, wherein the cross-linking agent is at least one of tetramethylethylenediamine, N' -methylenebisacrylamide; the initiator is at least one of ammonium persulfate, sodium persulfate and potassium persulfate.
4. The method for preparing anti-freeze conductive hydrogel with excellent mechanical properties according to claim 1, wherein the step S2 comprises:
s201: providing an etching solution and titanium aluminum carbide, adding the titanium aluminum carbide into the etching solution, uniformly mixing, reacting at the rotating speed of 400-1400 rpm for 5-20 min to obtain a first mixed solution, wherein the concentration of the titanium aluminum carbide in the first mixed solution is 0.01-0.25 g/L;
s202: and transferring the first mixed solution into a heater at the temperature of 25-60 ℃, condensing and refluxing at the stirring speed of 100-600 rpm, and etching to obtain the titanium carbide nanosheet dispersion.
5. The method for preparing anti-freeze conductive hydrogel with excellent mechanical properties according to claim 2, wherein the step S3 comprises:
s301: transferring the second clarified liquid into a reaction container, and mixing the second clarified liquid with the titanium carbide nanosheets to obtain a second mixed solution, wherein the mass ratio of the sodium alginate to the titanium carbide nanosheets is as follows: 1: 5-1: 1;
s302: putting the second mixed solution into a vacuum drier, and vacuumizing for 40-80 minutes to remove bubbles to obtain a third mixed solution;
s303: and transferring the third mixed solution into a mold, and putting the mold into a water bath to perform thermal polymerization for 40-80 min to obtain the conductive double-network hydrogel, wherein the thermal polymerization temperature is 40-90 ℃.
6. The preparation method of the antifreeze conductive hydrogel with excellent mechanical properties as claimed in claim 1, wherein the organic cryoprotectant solution is a mixture of cryoprotectant in deionized water, and the mass ratio of the cryoprotectant to the deionized water is 1: 1-5: 1; the cryoprotectant is at least one of ethylene glycol, glycerol and sorbitol.
7. The method for preparing anti-freeze conductive hydrogel with excellent mechanical properties of claim 1, wherein the halide concentration in the halide cryoprotectant solution is 0.05mol/L to 2 mol/L.
8. The method for preparing anti-freeze conductive hydrogel with excellent mechanical properties as claimed in claim 1, wherein the halide is at least one of lithium chloride, calcium chloride and sodium chloride.
9. An antifreeze conductive hydrogel with excellent mechanical properties, which is prepared by the method of any one of claims 1 to 8.
10. The application of the antifreeze conductive hydrogel with excellent mechanical property is characterized in that the application field comprises: environmental protection, energy storage, tissue engineering, tissue repair, human-computer interface and brain-computer interface.
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